CN101659861B

CN101659861B - Method for preparing petroleum sulfonate oil displacement agent

Info

Publication number: CN101659861B
Application number: CN 200810119472
Authority: CN
Inventors: 周云霞; 杨洪孝; 宋鸿远; 常松涛; 林宏海; 万影; 王玉华; 王玉梅
Original assignee: China Petroleum and Natural Gas Co Ltd
Current assignee: China Petroleum and Natural Gas Co Ltd
Priority date: 2008-08-29
Filing date: 2008-08-29
Publication date: 2012-12-12
Anticipated expiration: 2028-08-29
Also published as: CN101659861A

Abstract

The invention relates to a method for preparing a petroleum sulfonate oil displacement agent. Benzol-ketone dewaxing oil and furfural extract oil are mixed in a weight ratio of 1:0.01-1:0.5, and the mixture enters a film or tank reactor for sulfonation reaction; a sulfonating agent is SO3 gas, the concentration is diluted to between 1.5 and 3.0 percent in a volume ratio by dry air or inert gas of which the dew point is lower than 60 DEG C, the temperature of the sulfonation reaction is between 30 and 85DEG C, the acid value of sulfonatedbodies is controlled to between 30 and 90mgNaOH/g, and the sulfonatedbodies are neutralized by NaOH or KOH solution; and the raw materials have the advantages of high content of arene capable of being sulfonated and no coking phenomenon in the reaction process; after neutralization, and the sulfonatedbodies do not need extraction separation; the active matter content reaches 25 to 40 percent; a weak alkali/surfactant/polymer system configured by adopting Na2CO3 or a non-alkali binary system configured by salts such as NaCL and the like has the interfacial tension less than 10<-3>mN/m.

Description

A kind of preparation method of petroleum sulfonate oil displacement agent

Technical field

The present invention relates to a kind of through ketone benzene pressed distillate and furfural extract oil proportioning in the adjustment lubricating oil inverted sequence production technique; Be controlled at mixing raw material molecular weight and carbon number distribution between the certain limit, through the preparation method of oversulfonate, neutral petroleum sulfonate oil displacement agent.

Background technology

Adopt SO ₃As sulphonating agent, be that the technology of preparing of raw material production sulfonated petro-leum has had some reports with the fraction oil of petroleum.In order in sulfonation process, to avoid coking and to produce acid sludge; The general lower second line of distillation of aromaticity content that adopts perhaps subtracts three-way base oil as the sulfonation raw material; Major part was can not the sulfonated stable hydrocarbon during this raw material was formed, but sulfonated aromatic component content is below 20%.Oil field surfactant oil displacement product active matter content general requirement is more than 40%; So, need carry out extractive distillation after the sulfonation, tell unsulfonated oil; Improve the product actives; And the raw material aromaticity content has only 12.4%, even but the sulfonated aromatics conversion rate was greater than 40% o'clock in the raw material like this, and the acid sludge amount is still up to 4%--9% (as: CN1275431).This preparation technology's long flow path, preparation cost is higher, and how the unsulfonated oil that comes out of extracting and separating utilizes and become new problem.

The report preparation technology who has be with in crude oil or the fraction oil of petroleum sulfonation with sedimentation after, carry out extractive distillation to the upper and lower respectively and be processed into oil soluble, water-soluble sulfonate and carry out composite again.This method Production Flow Chart is long, complex process, and production cost is high, is not suitable for large-scale industrial production.

CN1203935 has reported the method that adopts crude oil or fraction oil of petroleum.2～8 reaction kettle polyphones of this process using have increased the appliance arrangement investment; This preparation method adopts-15 ℃～15 ℃ low temperature liquid-liquid sulfonation (liquid distillate oil and liquid sulphur trioxide), keep low-temp reaction and must set up the refrigerator cooling system; Improve flowability in reaction kettle and pipeline of raw material under the low temperature, slow down liquid SO ₃After getting into reaction kettle, the severe of reaction will be at liquid SO ₃The middle halocarbon diluent that adds relates to the recycling of thinner so in process of production, has increased energy consumption and production cost.

Summary of the invention

The object of the present invention is to provide a kind of sulfonation raw material that is used for the production fields oil-displacing agent through control molecular weight and carbon number distribution thereof; But this raw material has in sulfonated aromatic hydrocarbon content height, the noncoking of sulfonation reaction process, the sulfonated bodies and after not need extracting and separating both can obtain performance good, adaptable purpose product.

Be that directly to cut the molecular weight and the carbon number distribution of cut closely related with raw material for the surfactant oil displacement product performance of raw material with the fraction oil of petroleum.The present invention is through ketone benzene pressed distillate and furfural extract oil proportioning in the adjustment lubricating oil inverted sequence production technique; Setting range is: 1:0.01～1:0.5 (optimum is 1:0.1～1:0.25); Be controlled at 480～540 (optimum is 510～540) mixing sulfonation raw molecule amount, be controlled at C to this raw material carbon number distribution simultaneously ₂₂～C ₃₆Between, after oversulfonate, neutralization, can obtain the purpose product.The Na of this product ₂CO ₃Weak base ternary system system or NaCL binary do not have alkali systems, and to the crude oil and the sewage of grand celebration one factory of factory to six, IT all can reach 10 ^-3Below the mN/m.

1, sulfonation raw material simulation distil carbon number distribution is analyzed

TR ℃	361-369	369-391	391-412	412-431	431-449	449-466	466-481	481-496	496-509
										Carbon number distribution	21-22	22-24	24-26	26-28	28-30	30-32	32-34	34-36	36-38
Content %	1.2	8.5	14.7	19.7	19.3	16.5	10.8	6.8	2.2

2, the relation of sulfonation raw molecule amount and product performance

The fraction oil of petroleum of this product is extracted straight-chain paraffin (wax component) through ketone-benzol dewaxing device, improves aromatic component content.376～491 ℃ of its boiling range scopes, pour point are controlled at-6 ℃～-20 ℃, aromatic component content 30%～42%.The furfural extraction unit extracting and separating goes out to be rich in aromatic fraction, and furfural extract oil, its boiling range are 383～521 ℃, aromaticity content 55%～70%.Even the mixing sulfonation raw material heated and stirred of molecular weight ranges and carbon number distribution control stabilization, get into membrane type or tank reactor and carry out sulfonation reaction.Sulfonation temperature is 30 ℃～85 ℃, is preferably 60 ℃～70 ℃.The SO3 gas that sulphonating agent obtains with methods such as sulfur burning or oleum, liquid SO3 heating; Preferred combustion sulphur legal system is equipped with SO3 gas; Is (volume ratio) 1.5%～30% through dew point for dry air below-60 ℃ or inert gas dilution become concentration; Be preferably 3.5%～5.5%, feed sulfonation reactor.Its acid number of sulfonated bodies control is 30～90mgNaOH/g, and optimum is 60～70mgNaOH/g, through in NaOH or the KOH solution with after both obtained the purpose product.This product need not carry out extracting and separating, directly can be used as oil field three and adopt oil-displacing agent.This product actives (weighting method) content 25%～40% adopts Na ₂CO ₃The weak base ternary system of configuration perhaps adopts the binary of salt configurations such as NaCL not have alkali systems, and IT all can reach 10 ^-3Below the mN/m.

This invention has following characteristics:

1, adaptability to raw material is strong, adopts still formula sulphonator, film sulfonator all can produce.

2, this raw material have that but sulfonated aromatic hydrocarbon content is high, do not have in the reaction process in coking phenomenon, the sulfonated bodies and after do not need extracting and separating both can obtain the purpose product, product actives (weighting method) content reaches 25%～40%.

3, this method have that production technique is simple, production quality control characteristics stably.

4, the IT performance is good.Only this product has been carried out the interfacial activity detection, adopted Na with Daqing oil field oil extraction No.1 Factory to six factory crude oil, sewage ₂CO ₃The weak base ternary system of configuration perhaps adopts the binary of salt configurations such as NaCL not have the alkali systems IT all less than 10 ^-3Below the mN/m.

5, flexibility is strong.Product does not need composite other auxiliary agents, need not change system formulation, and to grand celebration 1 factory to-6 factory's crude oil, sewage that recover the oil, it is ultralow that the system IT all can reach.

Embodiment

The following example only is illustrative, and practical application not only is confined to this.

Embodiment 1:

Is the molecular weight after optimizing about 510, and carbon number distribution is at C ₂₂～C ₃₆Between the mixing raw material heated and stirred even, pour tank reactor into and carry out sulfonation reaction.The controlling reactor jacket temperature is 65-70 ℃, and the SO3 (volume) that feeds gas dense 7% carries out sulfonation reaction.Stopped reaction when acid number reaches 65mgNaOH/g adopts 35% (weight) NaOH solution to neutralize, and is 8-11 with the terminal point pH value in the control.Raw material and product detected result such as table 1, table 2.

Mixed feed components analytical table 1

Title	Stable hydrocarbon %	Aromatic hydrocarbons %	Nonhydrocarbon %	Bituminous matter %
					Mixing raw material	55.95	39.25	3.95	0.85

IT detects table 2

The grand celebration joint station polymer-bearing waste-water grand celebration four salt-resistant polymer 1200ppm of crude oil Daqing Refinery company of factory in four factory's apricots five that recover the oil

Embodiment 2:

Is the molecular weight after optimizing about 538, and carbon number distribution is at C ₂₂～C ₃₆Between the mixing raw material heated and stirred even, get into film reactor and carry out sulfonation reaction.Controlling its temperature of reaction is 55-60 ℃, and the SO3 (volume) that feeds gas dense 4.5% carries out sulfonation reaction, and tolerance is 2.5m3/h.Reaction back sulfonic acid acid number is 70mgNaOH/g, adopts 35% (weight) NaOH solution to neutralize, in the terminal point pH value for being controlled to be 8-11.Raw material and product detected result such as table 3, table 4.

Mixed feed components analytical table 3

Title	Stable hydrocarbon %	Aromatic hydrocarbons %	Nonhydrocarbon %	Bituminous matter %
					Mixing raw material	51.52	43.7	4.43	0.35

IT detects table 4

The grand celebration joint station polymer-bearing waste-water in four factory's apricots five that recovers the oil, grand celebration four factory's crude oil, the salt-resistant polymer 1200ppm of Daqing Refinery company

Embodiment 3:

The product of embodiment 2, adopt recover the oil crude oil, the sewage of three factories of grand celebration to be configured to yellow soda ash weak base ternary system, detected result is following:

Grand celebration three factories north, two western joint station polymer-bearing waste-water grand celebrations, the three salt-resistant polymer 1200ppm of crude oil Daqing Refinery company of factory that recover the oil

Embodiment 4:

The product of embodiment 2, adopt the recover the oil crude oil of three factories, the binary that sewage is configured to sodium-chlor of grand celebration not have alkali systems, detected result is following:

Embodiment 5:

Above-mentioned instance products obtained therefrom is carried out tensio-active agent lab simulation displacement of reservoir oil PT by following scheme.Testing program:

Table 5

Slug	IR PV	Injection system viscosity (mPa.s)	Scheme (effective concentration)
				Water drive to 98%
The ternary slug	0.3	40	1.2%Na2CO3+0.3% promoting agent+1550mg/L polymkeric substance
				Polymer slug	0.2	40	The 1150mg/L polymkeric substance

Imitation oil displacement experiment test-results: table 6

Claims

1. the preparation method of a petroleum sulfonate oil displacement agent is characterized in that: ketone benzene pressed distillate and furfural extract oil are pressed 1:0.01～1:0.5 weight mix, get into membrane type or tank reactor and carry out sulfonation reaction, sulphonating agent is SO ₃Gas; Is 1.5～30% through dew point for dry air below-60 ℃ or rare gas element are diluted to concentration by volume; Feed sulfonation reactor; The sulfonation reaction temperature is 30～85 ℃, and its acid number of sulfonated bodies control is 30～90mgNaOH/g, through in NaOH or the KOH solution with after promptly obtain the purpose product;

Ketone benzene pressed distillate: 376～491 ℃ of boiling range scopes, pour point be at-6 ℃～-20 ℃, aromatic component content 30%～42%;

Furfural extract oil, boiling range are 383～521 ℃, aromaticity content 55%～70%;

The mixing raw material molecular weight control is 480～540, and the raw material carbon number distribution is controlled at C ₂₂～C ₃₆Between.